Metal complexes

Abstract

The present invention relates to metal complexes and electronic devices, in particular organic electroluminescent devices containing said metal complexes. M(L)n(L′)m formula (1), formula (11)

1 - 16 . (canceled) 
     
     
         17 . A metal complex comprising at least one structure of the formula (1):
   M(L) n (L′) m   (1)
   wherein   M is iridium or platinum;   L is the same or different in each instance and is a bidentate ligand;   L′ is the same or different in each instance and is a ligand;   n is 1, 2 or 3;   m is 0, 1, 2, 3, or 4;   wherein two or more ligands L are optionally joined to one another or L is optionally joined to L′ by a single bond or a bivalent or trivalent bridge so as to define a tridentate, tetradentate, pentadentate, or hexadentate ligand system;   wherein the metal complex comprises at least one substructure of formula (2):   
       
         
           
           
               
               
           
         
         wherein
 the dotted bond denotes the linkage of this group to another part of the metal complex of formula (1); 
 X is the same or different in each instance and is CR or N, with the proviso that not more than three X per cycle are N; 
 R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R 1 ) 2 , CN, NO 2 , OH, COOH, C(═O)N(R 1 ) 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , C(═O)R 1 , P(═O)(R 1 ) 2 , S(═O)R 1 , S(═O) 2 R 1 , OSO 2 R 1 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group are optionally substituted by one or more R 1  radicals, wherein one or more nonadjacent CH 2  groups are optionally replaced by R 1 C═CR 1 , C≡C, Si(R 1 ) 2 , C═O, NR 1 , O, S, or CONR 1 , or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and optionally substituted in each case by one or more R 1  radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and optionally substituted by one or more R 1  radicals; and wherein two R radicals together optionally define a ring system; 
 R 1  is the same or different in each instance and is H, D, F, Cl, Br, I, N(R 2 ) 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein each alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is optionally substituted by one or more R 2  radicals, wherein one or more nonadjacent CH 2  groups are optionally replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , C═O, NR 2 , O, S, or CONR 2 , or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R 2  radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 2  radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 2  radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R 2  radicals; and wherein two or more R 1  radicals together optionally define a ring system; 
 R 2  is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by F, and wherein two or more R 2  radicals together optionally define a mono- or polycyclic ring system; 
 wherein the substructure, as well as the linkage denoted by the dotted bond, optionally have further bonds to parts of the metal complex of the formula (1); 
 
         with the proviso that if M is Ir, the part of the metal complex that binds to Ir comprises not more than one monodentate ligand L′ and the bidentate ligands L of the metal complex each have at least one Ir—C bond. 
       
     
     
         18 . The metal complex of  claim 17 , wherein the substructure of formula (2) is a substructure of at least one of formulae (2-1), (2-2), and/or (2-3): 
       
         
           
           
               
               
           
         
         wherein 
         g is 0, 1, 2, 3, 4, or 5; and 
         wherein the substructure, as well as the linkage denoted by the dotted bond, optionally have further bonds to parts of the metal complex of formula (1). 
       
     
     
         19 . The metal complex of  claim 17 , wherein the substructure of formula (2) is a substructure of formula (2-4): 
       
         
           
           
               
               
           
         
         wherein 
         g is the same or different in each instance and is 0, 1, 2, 3, 4 or 5; and 
         wherein the substructure, as well as the linkage represented by a dotted bond, may have further bonds to parts of the metal complex of the formula (1). 
       
     
     
         20 . The metal complex of  claim 19 , wherein the linkage, denoted by the dotted bond in formulae (2), (2-1), (2-2), (2-3), or (2-4), of the substructure of formulae (2), (2-1), (2-2), (2-3), and/or (2-4) is bonded to an aromatic or heteroaromatic ring system. 
     
     
         21 . The metal complex of  claim 20 , wherein the linkage, denoted by the dotted bond in formulae (2), (2-1), (2-2), (2-3), or (2-4), of the substructure of formulae (2), (2-1), (2-2), (2-3), and/or (2-4) is bonded to an aryl or heteroaryl radical of formula (Ar-1): 
       
         
           
           
               
               
           
         
         wherein 
         the dotted bonds denote the linkages of this group to other parts of the metal complex of the formula (1); 
         X a  is N, CR, or C if X a  denotes a bond to the substructure of formulae (2), (2-1), (2-2), (2-3), or (2-4) or to another part of the metal complex of formula (1); and 
         wherein the substructure, as well as the linkage denoted by the dotted bond, optionally has further bonds to parts of the metal complex of formula (1). 
       
     
     
         22 . The metal complex of  claim 20 , wherein the aromatic or heteroaromatic ring system bonded to the substructure of formula (2), (2-1), (2-2), (2-3), and/or (2-4) is bonded directly to the metal atom M. 
     
     
         23 . The metal complex of  claim 17 , wherein the metal is Ir(III) and the metal complex has three bidentate ligands, wherein the bidentate ligands coordinate to the iridium via one carbon atom and one nitrogen atom or via two carbon atoms. 
     
     
         24 . The metal complex of  claim 17 , wherein the metal is Pt and coordinates to two bidentate ligands. 
     
     
         25 . The metal complex of  claim 17 , wherein the metal complex comprises at least one bidentate ligand of formula (L-1), (L-2), and/or (L-3): 
       
         
           
           
               
               
           
         
         wherein 
         CyC is the same or different in each instance and is a substituted or unsubstituted aryl or heteroaryl group having 5 to 14 aromatic ring atoms and coordinates in each case to the metal via a carbon atom and which is bonded to CyD via a covalent bond in each case; 
         CyD is the same or different in each instance and is a substituted or unsubstituted heteroaryl group having 5 to 14 aromatic ring atoms and coordinates to the metal via a nitrogen atom or via a carbene carbon atom and which is bonded to CyC via a covalent bond; 
         wherein two or more ligands (L-1), (L-2), and/or (L-3) are optionally joined to one another via a single bond or a bivalent or trivalent bridge so as to define a tridentate, tetradentate, pentadentate, or hexadentate ligand system, wherein these optional bonds to a bridge are denoted by the dotted bond; and 
         wherein a substituent may also optionally coordinate to M. 
       
     
     
         26 . The metal complex of  claim 17 , wherein at least one bidentate ligand is selected from the group consisting of structures of formulae (L-1-1), (L-1-2), and (L-2-1) through (L-2-4): 
       
         
           
           
               
               
           
         
         wherein the at least one bidentate ligand coordinates to the metal at the position denoted by * and wherein the ligands are optionally bonded via a bridge, wherein the bond to the bridge is optionally via the position denoted by “o”; 
         and/or wherein at least one bidentate ligand is selected from the group consisting of structures of formulae (L-5) through (L-32): 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein the at least one bidentate ligand coordinates to the metal at the position denoted by * and wherein the ligands are optionally bonded via a bridge, wherein the bond to the bridge is optionally via the position denoted by “o”, and wherein the position denoted by “o” denotes a carbon atom if it constitutes a bridgehead site; 
         and/or wherein at least one bidentate ligand is selected from the group consisting of structures of formulae (L-35) through (L-40): 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein * denotes the position of coordination to the metal, and wherein the ligands are optionally bonded via a bridge, wherein the bond to the bridge is optionally via the position denoted by “o”; and 
         X is the same or different in each instance and is CR or N, with the proviso that not more than one X per cycle is N, wherein X is C if the ligand at this position is bonded to a bridge; 
         Y is the same or different in each instance and is CR 1  or N; 
         and/or wherein at least one bidentate ligand is selected from the group consisting of structures of formulae (L-41) through (L-45): 
       
       
         
           
           
               
               
           
         
         wherein the ligands (L-41) through (L-43) each coordinate to the metal via the nitrogen atom shown explicitly and the negatively charged oxygen atom and, for ligands (L-44) and (L-45), via the two oxygen atoms, and wherein the ligands are optionally bonded via a bridge, wherein the bond to the bridge is optionally via the position denoted by “o”, wherein X is C if the ligand is bonded to a bridge at this position, or, in formulae (L-44) or (L-45), the carbon atom optionally has a substituent R if the ligand is not bonded to a bridge at this position; 
         and/or wherein at least one bidentate ligand is selected from the group consisting of structures of formulae (L-46): 
       
       
         
           
           
               
               
           
         
         wherein * denotes the position of coordination to the metal, wherein the ligands are optionally bonded via a bridge. 
       
     
     
         27 . The metal complex of  claim 17 , wherein the metal complex is a metal complex of formula:
   Ir(L) n (L′) m   (1a)
   wherein the ligands L and L′ are bidentate ligands and are joined via a bridge so as to define a hexadentate tripodal ligand system, wherein the bridge via which the ligands are joined is a bridge of formula (3) or formula (4):   
       
         
           
           
               
               
           
         
         wherein 
         the dotted bond denotes the bond of the ligands to this structure; 
         X 1  is the same or different in each instance and is CR or N; 
         A 1  is the same or different in each instance and is C(R) 2  or O; 
         A 2  is the same or different in each instance and is CR, P(═O), B, or SiR, with the proviso that, when A 2 =P(═O), B, or SiR, A 1  is O and the A bonded to this A 2  is not —C(═O)—NR′— or —C(═O)—O—; 
         A is the same or different in each instance and is —CR═CR—, —C(═O)—NR′—, —C(═O)—O—, or a group of formula (5): 
       
       
         
           
           
               
               
           
         
         
           wherein the dotted bond denotes the position of the bond of the ligands to this structure and * denotes the position of the linkage of the unit of formula (5) to the central cyclic group; 
           X 2  is the same or different in each instance and is CR or N or two adjacent X 2  together are NR, O, or S, so as to define a five-membered ring, and the remaining X 2  are the same or different in each instance and are CR or N; or two adjacent X 2  together are CR or N when one X 3  in the cycle is N, so as to define a five-membered ring; with the proviso that not more than two adjacent X 2  are N; 
           X 3  is C in each instance or one X 3  is N and the other X 3  in the same cycle is C; with the proviso that two adjacent X 2  together are CR or N when one X 3  in the cycle is N; 
           R′ is the same or different in each instance and is H, D, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group in each case is optionally substituted by one or more R 1  radicals and wherein one or more nonadjacent CH 2  groups are optionally replaced by Si(R 1 ) 2 , or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R 1  radicals; and 
         
         wherein the three bidentate ligands L and/or L′, apart from via the bridge of the formula (3) or (4), are optionally also ring-closed via a further bridge to form a cryptate. 
       
     
     
         28 . An oligomer, polymer, or dendrimer comprising one or more metal complexes of  claim 17 , wherein one or more bonds of the one or more metal complexes to the polymer, oligomer, or dendrimer are present. 
     
     
         29 . A formulation comprising at least one metal complex of  claim 17  and at least one further compound selected from the group consisting of solvents, fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials. 
     
     
         30 . A formulation comprising at least one oligomer, polymer, or dendrimer of  claim 28  and at least one further compound selected from the group consisting of solvents, fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials. 
     
     
         31 . A process for preparing the metal complex of  claim 17  comprising reacting a metal complex with an aromatic or heteroaromatic compound. 
     
     
         32 . A process for preparing the oligomer, polymer, or dendrimer of  claim 28  comprising reacting a metal complex with an aromatic or heteroaromatic compound. 
     
     
         33 . An electronic device comprising at least one metal complex of  claim 17 . 
     
     
         34 . The electronic device of  claim 33 , wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, oxygen sensors, oxygen sensitizers, and organic laser diodes. 
     
     
         35 . An electronic device comprising at least one the oligomer, polymer, or dendrimer of  claim 28 . 
     
     
         36 . The electronic device of  claim 35 , wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, oxygen sensors, oxygen sensitizers, and organic laser diodes.